Process for the preparation of aziridine phosphoryldifluorides



V wherein R R R and United States Patent M 3 168 514 PROCESS FOR THEPREPARATION or AZIRIDINE PHOSPHORYLDIFLUORIDES William C. Preusse,Naperville, Ill., assignor to Olin Mathieson Chemical Corporation, NewHaven, Conn., a corporation of Virginia 1 N0 Drawing. Filed Aug. 26,1963, Ser. No. 304,615 3 Claims. (Cl. 260-239) desired by the slowdropwise addition of the ethylenimine Under these circumstances, areaction 0 t0 the P203F4. temperature of upto about 70 C. can beutilized. However, the reaction is vigorously exothermic, and apreferred process embodiment utilizes an inert organic diluent orsolvent since the temperature of the reaction For example,2,2-dimethylmixture may then be more conveniently adjusted andcontrolled. The use of a diluent or solvent is also preferred since inthe preparation of a mole of l-aziridinyl phosphoryldifluoride, there isalways formed a mole of 1 aziridinium ,difluorophosphate, and this saltcan be more readily removed from the reaction mixture by a conventionaltechnique such as filtration when a diluent hasbeen utilized in thereaction mixture. Suitable diluents for use in the process of thisinvention include ether, chloroform and the like. It is preferred toutilize a process temperature range of about 10 C. or less during thepreparation of the difluorides, and the temperature may be kept at thislevel by using an ice bath. 'The following example will serve toillustrate the preparation of a compound having the Formula I whereinethylenimine is reacted with P O F This invention relates to novell-aziridinyl phosphoryldifluorides, and more particularly it relates tocompounds having the following general formula:

from the class consisting of a hydrogen atom, an alkyl R, areindependently selected.

Patented Feb. 2, 1 9

. 2 hydride as describedby E. A. Robinsonin the Journal of Chemistry,40, 1729 (1962).

Example 1 68.0 g. (0.365 mole) of freshly distilledpyrophosphoryltetrafluoride was dissolved in approximately 400 cc. ofanhydrous ether. The solution was placed in a one liter three-neckedflask equipped with stirrer and dropping funnel, and the flask waspacked in ice. Then 31.5 g.

Canadian (0.733 mole) of ethylenimine in 100 mls. of anhydrous ether wasadded dropwise to the reaction flask with stirring over a one hourperiod with the reaction temperature being maintained at 0-10 C. Thereaction mixture was allowed to stand for one hour longer, and then asolid precipitate was removed by filtration. The dried solid had amelting point of 98 C. The following analytical data revealed that1-aziridinium difluorophosphate had been obtained. Yield: 99.0%.

Anal.-Calcd. for NH PO F C, 16.5; H, 4.13; N,

9.65; P, 21.4; F, 26.2. Found: C, P, 20.65; F, 26.6. ,7 V V The etherfiltrate was fractionally distilled, and a colorless material boiling at44 C./26 mm. was obtained. The

following analytical data revealed that l-aziridinylphosphoryldifiuoride had been obtained in good yield.

Analysis-Called. for DNPOF C, 18.9; H, 3.15; N, 11.0; P, 24.4; F, 29.0.Found: C, 19.2; H, 3.12; N, 10.5; P, 24.0; F, 30.1.

Confirmation that the ethylenimine ring remained intact in thesecompounds was obtained by infrared and nuclear magnetic resonanceanalyses.

As noted in the preceding discussion, the l-aziridinylphos'phoryldifluorides of the general Formula I are characterized byunusualbiological activity, and they are useful in the area ofcontrolling harmful insects. They are. active chemosterilants, and theycan be utilized as the chief active ingredient in a variety ofpest-steril-ant compositions wherein they are admixed suitableadjuvants. For example, baits containing these compounds as the activeingredient, especially with a sugar carrier, have been found to beeffective sterilant compositions when administered to housefli-es.Subsequent observation 55 group, e.g. methyl, ethyl, 'propyl andbutyl,and anarylf group such as phenyl group! These compounds are bio- 3logically active and are useful for combating harmful" insects.

"r The compounds having the'Formula I arefprepared by" the reaction ofpyrophosphoryltetrafluoride with ethylenimine and its homologs inaccordance with the following Pyrophosphoryltetrafluoride (P 0 1 isprepared by the reaction of difiuorophosphoric acid and phosphoric. an-

, wherein R R R andR lare selected from the'class 9 consisting ofhydrogen, alkyl having 1-4carbon atoms, f

of fly eggs collected from oviposition sites revealed a high degree ofnon-hatchihgor sterile eggs. The compounds (I) also are valuableinsecticides; When the aforementioned bait was fed to houseflies, a highpercentage of fly mortality was obtained even at very low concentrationsof active ingredient.

What is claimed is:

1. A process for preparing .laziridinyl phosphoryldia fluorides whichcomprises reacting pyrophosphoryltetrafluoride with a compound havingthe formula .1 /G R2 i and phenyl.

2. A process for preparing' 1-aziridinyl,phosphoryldi- V fluorides'whichcomprises reacting pyrophosphoryltetrafluoride with a compound havingthe formula wherein R1, R R and R are selected from the class Consistingof hydrogen, alkyl having 1-4 carbonatoms, and phenyl in the presence ofan inert organic diluent.

3. A process for preparing l-aziridinyl phosphoryldiwherein R R R and Rare selected from the class consisting of hydrogen, alkyl having 1-4carbon atoms, and phenyl in the presence of an inert organic diluent ata temperature of less than about 10 C., removing the formedl-aziridinium difluorophosphate from the reaction mixture, andrecovering the l-aziridinyl phosphoryldifluoride.

References Cited bythe Examiner UNITED STATES PATENTS 2,606,902 8/ 52Parker et a1. 260- 239 IRVING MARCUS, Primary Examiner.

NICHOLAS S. RIZZO, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3, 168,514 February 2, 1965 William C. Preusse It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Column 1, lines 12 and 13, after "2,3-dimethylethylenimine," insert2,S-diphenyl-ethylenimine, same column 1, line 10, beginning with "Anumber of" strike out all to and including "with P 0 1 in line 42, samecolumn 1,

and insert the same after "(1962)." in line 2, column 2; column 1, line57, after "as" insert a Signed and sealed this 29th. day of June 1965..

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Aitesting Officer Commissioner ofPatents

1. A PROCESS FOR PREPARING 1-AZIRIDINYL PHOSPHORYLDIFLUORIDES WHICHCOMPRISES REACTING PYROPHOSPHORYLTETRAFLUORIDE WITH A COMPOUND HAVINGTHE FORMULA